Preparation of monomers

ABSTRACT

Organic compounds having aromatic ester, thioester, or carbonate groups are prepared by reacting an organometallic reactant where the metal is germanium, tin, lead, gallium, indium, thallium, arsenic, antimony, or bismuth with a suitable second reactant. For example, the ester ##STR1## is prepared by reacting the bis-tri--n-butyl tin derivative of ethyl 4-hydroxybenzoate with 4-phenoxybenzoyl chloride.

This application is a divisional of Application Ser. No. 07/204,650,filed July 29, 1988, now U.S. Pat. No. 4,841,094 which is a divisionalof Application Ser. No. 06/877,658, filed June 3, 1986, now U.S. Pat.No. 4,777,282, the disclosures of which are incorporated herein byreference.

This invention relates to the preparation of organic compounds andespecially to the preparation of monomers for subsequent use inpolymerisation reactions.

Known industrial methods for producing monomers, especially aromaticmonomers wherein an aromatic group is bonded directly to a functionalgroup such as an ester, thioester or carbonate, often have a number ofdisadvantages. For example high temperatures are usually required and/orunpleasant solvents such as pyridine are necessary. Aromatic estermonomers, for example can be prepared using a phase-transfer catalysismethod, but this method has the disadvantage that two or morerecrystallisations of the product are usually necessary in order toobtain a satisfactorily pure monomer.

In a paper by J Valade and M Pereysf entitled `Etude de la scission dela liaison Sn-O-C dans les monoalcoxytrialcoyetains`, Compte. Rend.254,3693 (1962) there is described a method for making simple aliphaticesters by reacting methoxytributyltin with acetyl chloride or benzoylchloride, the reaction producing methyl acetate or methyl benzoate. Theuse of tin in intermediates for making polymers is described in EuropeanPatent Publication No. 0,154,506.

In a first aspect the present invention provides a method for thepreparation of an organic compound comprising reacting a first compoundof the formula:

    (R).sub.r --M--Y--A.sup.1 --Y--M--(R).sub.r

where

each R is independently a substituted or unsubstituted alkyl or arylgroup;

each r is independently an integer from 1 to 4 inclusive depending uponthe element M used;

each M is independently an element selected from Group IIIB, IVB or VBof the Periodic Table (IUPAC 1965 revision) or a transition metal,excluding carbon, silicon, nitrogen, phosphorus, boron, aluminium andtitanium;

each Y is independently an oxygen atom, a sulphur atom, a substitutednitrogen atom other than ##STR2## or a substituted phosphorus atom otherthan ##STR3## and A¹ is an aromatic, aliphatic, aromatic/aliphatic,heterocyclic, alicyclic, siloxyl or silane group,

with a second compound of the formula: ##STR4## where X is a halogenatom or a group capable of reacting with the first compound to eliminatea compound containing M and X;

B is an atom selected from carbon, phosphorus, sulphur or silicon;

D is an oxygen or sulphur atom or an amine group;

d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if Bis sulphur or zero if B is silicon;

E is selected from an aromatic group, aliphatic group, OR' or NR'₂ if Bis phosphorus, or from an aromatic group, aliphatic group or --OR' if Bis silicon, where R' is a substituted or unsubstituted alkyl or arylgroup;

e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B issilicon; and

A² is an aromatic, aliphatic, aromatic/aliphatic, heterocyclic,alicyclic, siloxyl or silane group,

to eliminate the compound (R)_(r) MX and produce a compound of theformula: ##STR5## where G is either the group --M--(R)_(r), or the group##STR6##

Preferably the stoichiometric ratio of the first compound to the secondcompound is 1:2 to produce a compound, usually a monomer, of theformula: ##STR7## An example of this reaction is as follows: ##STR8##

In a second aspect the present invention provides a method for thepreparation of an organic compound comprising reacting a first compoundof the formula:

    (R).sub.r --M--Y--A.sup.1 --Y--M--(R).sub.r

where

each R is independently a substituted or unsubstituted alkyl or arylgroup;

each r is independently an integer from 1 to 4 inclusive depending uponthe element M used;

each M is independently an element selected from Group IIIB, IVB or VBof the Periodic Table (IUPAC 1965 revision) or a transition metal,excluding carbon, silicon, nitrogen, phosphorus, boron, aluminium andtitanium;

each Y is independently an oxygen atom, a sulphur atom, a substitutednitrogen atom other than ##STR9## or a substituted phosphorus atom otherthan ##STR10## and A¹ is an aromatic, aliphatic, aromatic/aliphatic,heterocyclic, alicyclic, siloxyl or silane group,

with a second compound of the formula: ##STR11## where X is a halogenatom or a group capable of reacting with the first compound to eliminatea compound containing M and X;

B is an atom selected from carbon, phosphorus, sulphur or silicon;

D is an oxygen or sulphur atom or an amine group;

d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if Bis sulphur or zero if B is silicon;

E is selected from an aromatic group, aliphatic group, OR' or NR'₂ if Bis phosphorus, or from an aromatic group, aliphatic group or --OR' if Bis silicon, where R' is a substituted or unsubstituted alkyl or arylgroup;

e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B issilicon; and

p is zero or 1,

to eliminate the compound (R)_(r) MX and produce a compound of theformula: ##STR12## where Q is the either the group (R)_(r) M-, or thegroup ##STR13## and T is either the atom or group X, or the group--Y--A¹ --Y--M--(R)_(r).

The method according to this second aspect is especially useful when itis desired to produce a monomer having reactive end groups of the type(R)_(r) M-or ##STR14## which can then be used directly in polymerisationreactions. An especially preferred monomer is one having acid chloride,##STR15## end groups.

When carrying out the method according to the second aspect of theinvention, the reaction conditions should be selected so as to prevent apolymerisation reaction between the first and second compounds.Therefore it is preferred to add a solution of the first compoundgradually, for example dropwise, to a solution of the second compound.Also it is preferred that the reaction is carried out in a solvent inwhich the product is substantially insoluble so that the productprecipitates out of solution once it is formed.

When p is zero, the second compound being phosgene for example, thereaction produces a compound wherein the group ##STR16## is bonded atboth sides to a Y atom, such as in a carbonate. However, it is generallypreferred that p is 1 and examples of reactions according to the secondaspect of the invention are as follows: ##STR17##

The first compound may also be `polymeric` and thus a third aspect ofthe present invention provides a method for the preparation of anorganic compound comprising reacting a first compound of the formula:##STR18## where R is independently a substituted or unsubsituted alkylor aryl group;

r' is independently zero or an integer from 1 to 3 depending upon theelement M used;

each Y is independently an oxygen atom, a sulphur atom, a substitutednitrogen atom other than ##STR19## or a substituted phosphorus atomother than ##STR20## A¹ is an aromatic, aliphatic, aromatic/aliphatic,heterocyclic, alicyclic, siloxyl or silane group, and

x is an integer greater than 1,

with a second compound of the formula: ##STR21## where X is a halogenatom or a group capable of reacting with the first compound to eliminatea compound containing M and X;

B is an atom selected from carbon, phosphorus, sulphur or silicon;

D is an oxygen or sulphur atom or an amine group;

d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if Bis sulphur or zero if B is silicon;

E is selected from an aromatic group, aliphatic group, OR' or NR'₂ if Bis phosphorus, or from an aromatic group, aliphatic group or --OR' if Bis silicon, where R' is a substituted or unsubstituted alkyl or arylgroup;

e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B issilicon; and

A² is an aromatic, aliphatic, aromatic/aliphatic, heterocyclic,alicyclic, siloxyl or silane group,

to eliminate the compound ##STR22## and produce a compound of theformula: ##STR23##

Many different types of compounds can be prepared by the methodaccording to any of the above aspects of the invention. These include,for example, esters, thioesters, amides, thioamides, imides, thioimides,carbonates, thiocarbonates and urethanes, but preferably esters,thioesters, carbonates or thiocarbonates are prepared. Therefore it ispreferred that the group ##STR24## is a carbonyl ##STR25## group or athiocarbonyl ##STR26## group, more preferably a carbonyl group, and thatthe atom Y is an oxygen or sulphur atom, more preferably an oxygen atom.The methods of the invention are especially advantageous for thepreparation of aromatic esters, aromatic thioesters, aromatic carbonatesor aromatic thiocarbonates, these being difficult to produce by knowncommercial methods. By `aromatic ester`, `aromatic thioester`, etc, ismeant a compound containing an ester group, thioester group, carbonategroup or thiocarbonate group bonded to an aromatic group, for example##STR27##

Thus it is preferred that the group A¹ in the first compound is partlyaromatic and each atom Y is bonded to an aromatic group of A¹. It isespecially preferred that the compound produced by the reaction containsan ester, thioester, carbonate or thiocarbonate group that is bonded onboth sides to an aromatic group; that is to say the resulting compoundcontains, for example, an aromatic ester group ##STR28##

Aromatic esters, thioesters, carbonates or thiocarbonates may beprepared by reacting a difunctional compound containing two (R)_(r) M-groups or a polymeric compound containing the repeat unit ##STR29## asdefined in the above aspects of the invention, or they may be preparedby reacting a monofunctional compound containing only one (R)_(r) -M-group with a second compound which may be either mono- or difunctional.

Accordingly, in a fourth aspect the present invention provides a methodfor the preparation of an aromatic ester, aromatic thioester, aromaticcarbonate or aromatic thiocarbonate compound comprising reacting a firstcompound of the formula: ##STR30## where each R is independently asubstituted or unsubstituted alkyl or aryl group;

r is an integer from 1 to 4 inclusive depending upon the element M used;

M is an element selected from Group IIIB, IVB or VB of the PeriodicTable or a transition metal, excluding carbon, silicon, nitrogen,phosphorus, boron, aluminium and titanium;

Z¹ is an oxygen or a sulphur atom, and;

A³ is an aromatic, aliphatic, aromatic/aliphatic, heterocyclic,alicyclic, siloxyl or silane group, or a hydrogen atom

with a second compound of the formula: ##STR31## where X is a halogenatom or a group capable of reacting with the first compound to eliminateM and X;

Z² is either an oxygen or a sulphur atom; and

J is either the atom or group X, or

the group A² where A² is an aromatic, aliphatic, aromatic/aliphatic,heterocyclic, alicyclic, siloxyl or silane group, or

the group ##STR32## where A⁴ is an aromatic, aliphatic,aromatic/aliphatic, heterocyclic, alicyclic, siloxyl or silane group,

to eliminate the compound (R)_(r) MX and produce an aromatic ester,aromatic thioester, aromatic carbonate or aromatic thiocarbonatecompound of the formula: ##STR33## where L is either the atom or groupX, the group

A², the group ##STR34## or the group ##STR35##

The preferred stoichiometric ratio of the first compound to the secondcompound according to the fourth aspect of the invention is either 1:1or 2:1. If a stoichiometric ratio of 1:1 is chosen the second compoundmay be of the formula: ##STR36## and reaction of the two compoundsproduces a compound of the formula: ##STR37## An example of thisreaction is: ##STR38##

Alternatively the second compound may be of the formula: ##STR39## toproduce, again using a stoichiometric ratio of first to second compoundsof 1:1, a compound of the formula: ##STR40## An example of this reactionis: ##STR41##

To prevent the product from reacting with a further molecule of thefirst compound it is preferred that the first and second compounds arereacted together by gradually adding, for example in drops, a solutionof the first compound to a solution of the second compound, and alsothat the reaction is carried out in a solvent in which the compoundproduced by the reaction is substantially insoluble so that itprecipitates out of solution once it is formed.

In another alternative the second compound may be of the formula##STR42## to produce a monomer of the formula: ##STR43## An example ofthis reaction is: ##STR44##

If a stoichiometric ratio of 2:1 is used in the method according to thefourth aspect of the invention, the second compound is preferably of theformula: ##STR45## the reaction of first and second compounds thenproducing a monomer of the formula: ##STR46## An example of thisreaction is: ##STR47##

Preferably in the resulting compound the ##STR48## group is bonded onboth sides to an aromatic group. Therefore it is preferred that the A²and A⁴ groups in the second compounds are each at least partly aromatic,and the ##STR49## group is bonded to an aromatic group of the A² or A⁴group. Thus the compound produced by the reaction preferably contains agroup of the formula ##STR50## Preferably both Z¹ and Z² are oxygenatoms, the reaction between the first and second compounds thereforeproducing an aromatic ester.

Hereinafter the description of the invention relates to all aspects ofthe invention unless otherwise specified.

The method according to the invention is especially advantageous for thepreparation of compounds wherein at least one end group, and preferablyboth end groups, are aromatic, for example a phenyl group. Suchcompounds are useful as monomers which can be polymerised with one ormore other types of monomers, or with themselves, to form, for example,polyesters or polyetheresters. However, the method according to theinvention may also be used for the preparation of compounds which arenot for subsequent use in polymerisation reactions.

One advantage of the invention is that compounds can often be preparedusing relatively low reaction temperatures, usually between -30 degreesand 150 degrees C. (although it is to be understood that higher andlower temperatures can also be used). The use of low temperaturesenables thermally sensitive groups to be included in the compound, forexample carbon-carbon double and triple bonds.

Another advantage is that the reagents and solvents used in the reactioncan be chosen to be relatively non-hazardous. Also the eliminatedcompounds or by-product, (R)_(r) MX, of the reaction is generallysoluble in many solvents, making purification of the resulting compoundan unusually easy task. Furthermore this by-product may form a startingreagent for the preparation of the first compound.

Preferably the element M in the first compound is selected from GroupIVB of the Periodic Table and is in oxidation state (+4). Morepreferably M is either tin or germanium, and tin (+4) is especiallypreferred.

Suitable groups for R include unsubstituted alkyl groups such as methyl,ethyl, propyl, butyl, pentyl, octyl etc., substituted alkyl groups suchas benzyl or phenylethyl, or a substituted or unsubstituted aryl groupsuch as phenyl, naphthyl or biphenyl. Preferably, however, R is an alkylgroup containing 3 or 4 carbon atoms, an n-butyl group being especiallypreferred. The number, r, of R groups attached to the element M dependsupon the valency of the element M; for example when M is tin (+4) then ris 3. Thus in the first and second aspects of the invention the firstcompound preferably has the formula Bu₃ Sn-Y-A¹ -Y-SnBu₃, and in thethird aspect the first compound preferably has the formula ##STR51##

There are many groups suitable for use as the A¹, A², A³ and A⁴ groupsof the first and second compounds. As stated above these are selectedfrom an aromatic, aliphatic, aromatic/aliphatic, heterocyclic,alicyclic, siloxyl or silane group, or for A³ a hydrogen atom. Thisincludes substituted or unsubstituted groups, heteroaromatic,heteroaliphatic and multiple aromatic groups which may be joined by anoxygen or sulphur atom or sulphone, imide or ketone group for example.The A¹ and A⁴ groups are difunctional, the A¹ group being bonded at eachend to a Y atom or group, and the A⁴ group being bonded at each end to a##STR52## group or ##STR53## group. The A² and A³ groups aremonofunctional and, as mentioned above, it is preferred that the end ofthe A² or A³ group remote from the B or Z¹ atom respectively isaromatic. The following list gives examples of suitable groups for themonofunctional A² and A³ groups. Similar groups are also suitable for A¹and A⁴ by removal of a hydrogen atom, thus providing a difunctionalgroup. ##STR54##

These examples listed for the A groups are bonded to the B or Y atomwith an aromatic carbon atom. However groups may also be chosen for anyone of the A groups wherein an aliphatic carbon atom or a silicon atomis bonded to the Y atom of the first compound or the B or C atom of thesecond compound as appropriate. Also the A² and A⁴ groups may contain anoxygen, nitrogen or sulphur for example which bonds to the B or C atomrespectively in the second compound in the first, second or thirdaspects of the invention.

Typical solvents used in the process of the present invention include,for example, chloroform, xylene, toluene, tetrahydrofuran,chlorobenzene, 1,2-dichloroethane, benzophenone, diphenylsulphone, ormixtures thereof, although it should be remembered that when thecompound produced has end groups of the formula (R)_(r) M- or -X thenthe solvent chosen should be one in which the compound produced issubstantially insoluble.

Once the compound has been isolated it is possible for the by-product tobe easily removed, for example by extraction with acetone, hexane,methanol or other simple solvents which do not affect the resultingcompound adversely. The by-product can then be recovered by distillationor crystallisation for example.

There are a number of possible routes for preparing the first compoundfor the method according to the invention. In the first aspect of theinvention the first compound, for example Bu₃ SnO-A¹ -OSnBu₃, may beprepared by reaction of Bu₃ SnOMe with HO-A¹ -OH. Similarly in thesecond aspect of the invention the first compound, for example ##STR55##may be prepared by reaction of Bu₃ SnOMe with ##STR56##

The invention will now be illustrated by the following examples.

EXAMPLE 1

To 400 mls of xylene was added 50 g of thiophenol and 135.3 g ofbis(tributyltin)oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed heating was discontinued and when refluxing hadsubsided 46.06 g of isophthaloyl dichloride added. This produced aslight yellowing of the solution. The mixture was then heated to refluxfor 3 hours and then allowed to cool. The colourless crystalline productwas collected by filtration, washed with cold toluene and dried. Afurther crop of crystals was obtained by concentrating the motherliquors.

Yield was 76.5 g, 96%,

The product was identified as ##STR57##

The analogous terephthaloyl product was prepared by repeating the abovereaction, replacing the isopthaloyl dichloride with terephthaloyldichloride.

EXAMPLE 2

To 225 mls of xylene was added 5.50 g of hydroquinone and 29.81 g ofbis(tributyltin)oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed heating was discontinued and when refluxing hassubsided 24.43 g of 4-phenoxybenzoyl-chloride added. The mixture wasthen heated to reflux for 3 hours and then allowed to cool. Thecolourless crystalline product was collected by filtration, washed withcold toluene and dried. A further crop of crystals was obtained byconcentrating the mother liquor.

Yield was 24.0 g, 90%.

The product was identified as ##STR58##

This monomer may be reacted with a mixture of terephthaloyl andisophthaloyl chlorides in 1,2-dichloroethane together withN,N-dimethylformamide and aluminium chloride to produce a polymer of therepeat unit: ##STR59##

EXAMPLE 3

To 125 mls of xylene was added 6.0 g of phenoxyphenol and 9.60 g ofbis(tributyltin)oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed heating was discontinued and when refluxing hadsubsided 3.27 g of terephthaloyl chloride added. The mixture was heatedto reflux for 3 hours and then allowed to cool. The colourlesscrystalline product was collected by filtration, washed with coldtoluene and dried. A further crop of crystals was obtained byconcentrating the mother liquor.

Yield 7.5 g, 91%.

The product was identified as ##STR60##

The analogous isophthaloyl product was prepared by repeating the abovereaction, replacing the terephthaloyl dichloride with isophthaloyldichloride.

This monomer may be reacted with a mixture of terephthaloyl andisophthaloyl chloride in 1,2-dichloroethane together withN,N-dimethylformamide and aluiminium chloride to produce a polymer ofthe repeat unit: ##STR61##

EXAMPLE 4

To 500 mls of toluene was added 15.32 g of bisphenol A and 43.1 g oftributyltinmethoxide. The reaction was heated to boiling and using afractionating column methanol was removed. When all the methanol hadbeen removed heating was discontinued and when refluxing had subsided18.86 g of benzoylchloride added. The mixture was then heated to refluxfor 3 hours and then allowed to cool. The colourless crystalline productwas collected by filtration, washed with cold toluene and dried. Afurther crop of crystals was obtained by concentrating the motherliquors.

Yield 27.2 g, 93%.

The product was identified as ##STR62##

The above reaction was repeated a number of times, the bisphenol A beingreplaced in each repeated reaction with a different compound asindicated below:

a) replacing bisphenol A with hydroquinone to produce the monomer##STR63##

b) replacing biphenol A with methylhydroquinone to produce the monomer##STR64##

c) replacing bisphenol A with 4,4'-dihydroxydiphenyl ether to producethe monomer ##STR65##

d) replacing bisphenol A with 4,4'-dihydroxybiphenyl to produce themonomer ##STR66##

EXAMPLE 5

To 100 mls of xylene was added 3.1 g of methylhydroquinone and 14.70 gof bis(tributyltin)oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed heating was discontinued and when refluxing hadsubsided 9 g of 4-n-propylbenzoyl chloride added. The mixture was thenheated to reflux for 3 hours. The pale yellow solution was concentratedon a rotary evaporator leaving a yellow oil. This was dissolved inmethylcyclohexane and cooled to -15° C. to give a colourless,crystalline product.

Yield 9 g, 86%.

The product was identified as ##STR67##

EXAMPLE 6

To 200 mls of toluene was added 13.84 g of 4-bromophenol and 23.84 g ofbis(tributyltin)oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed heating was discontinued and when refluxing hadsubsided 8.12 g of terephthaloyl chloride added. The mixture was thenrefluxed for two hours and then allowed to cool. The white crystallineproduct was collected by filtration, washed with cold toluene and dried.A further crop of crystals was obtained by concentrating the motherliquor.

Yield 17.68 g, 93%.

The product was identified as, ##STR68##

EXAMPLE 7

To 150 m mls of toluene was added 6.61 g of hydroquinone and 35.76 g ofbis(tributyltin)oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed heating was discontinued and when refluxing hadsubsided 19.03 g of p-fluorobenzoyl chloride added. The mixture wasrefluxed for one hour and then allowed to cool. The white crystallineproduct was collected by filtration, washed with cold toluene and dried.A further crop of crystals was obtained by concentrating the motherliquor.

Yield 19.89 g 93.5%.

The product was identified as, ##STR69##

EXAMPLE 8

To 150 m mls toluene was added 9.97 g of ethyl-4-hydroxybenzoate and17.88 g of bis(tributyltin)oxide. The reaction mixture was heated toboiling and water of reaction removed using a Dean-Stark head. After allthe water had been removed heating was discontinued and when refluxinghad subsided 27.92 g of 4-phenoxybenzoyl chloride added. The mixture wasrefluxed for one hour and then allowed to cool. No precipitate formed oncooling. The toluene was removed under reduced pressure and replaced byhexane. After cooling to -18° C. a white crystalline product wasobtained. A further crop of crystals was obtained by concentrating themother liquor. This material was very soluble at room temperature in anumber of solvents.

Yield 37.40 g 86%.

The product was identified as ##STR70##

EXAMPLE 9

To 150 mls of toluene was added 5.51 g of hydroquinone and 29.80 g ofbis(tributyltin)oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After allowing tocool the solution was transferred to a dropping funnel equipped with apressure equalising side arm. This solution was then slowly added to analmost refluxing solution of 30.45 g of terephthaloyl chloride in 150mls of toluene. After the addition was complete the mixture was refluxedfor 2 hours and then allowed to cool. The white crystalline product wascollected by filtration washed with cold toluene and dried.

Yield 20 g 88%.

The product was identified as ##STR71##

EXAMPLE 10

To 200 ml of toluene was added 20.43 g of 4-phenylphenol and 35.76 g ofbis(tributyltin) oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed the reaction mixture was allowed to cool. When cool thesolution was transferred to a dropping funnel fitted with a pressureequalising side arm. This solution was then slowly added to a warmsolution of 48.72 g of terephthaloyl chloride in 150 mls of toluene.After the addition was complete the mixture was heated to reflux for onehour and then allowed to cool. The pale yellow crystalline product wascollected by filtration washed with cold toluene and dried.

Two products were identified: ##STR72## 34.29 g, 85% yield. ##STR73##10% yield.

The product ##STR74## was prepared in a similar manner.

EXAMPLE 11

To 200 mls of toluene was added 16.52 g of hydroquinone and 89.41 g ofbis(tributyltin)oxide. The reaction mixture was heated to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed heating was discontinued. One the temperature of thesolution had droped to 80° C. a solution of 12.18 g of terephthaloylchloride in 50 mls of toluene was slowly added over 45 minutes. Afterthe addition was complete the whole mixture was refluxed for 2 hours.Once cool the toluene was removed and replaced with 200 mls of methanolplus 20 mls of a 50% solution of a hydrochloric acid. The white solidwas collected by filtration and washed with 300 mls of methanol at 50°C.

Yield 16.40 g 80%.

The product was identified as ##STR75##

EXAMPLE 12

To 150 mls of toluene was added 10 g of 4-phenoxyphenol and 16.00 g ofbis(tributyltin)oxide. The reaction mixture was heating to boiling andwater of reaction removed using a Dean-Stark head. After all the waterhad been removed heating was discontinued and the mixture allowed tocool to room temperature. Once cool a solution of 2.66 g of phosgene in18 mls of toluene was slowly added. Upon completion of the addition themixture was stirred at room temperature for 1 hour and then at refluxfor 1 hour. After cooling to -18° C. the white crystalline solid wascollected by filtration washed with cold toluene and dried.

Yield 9.6 g 89%.

The product was identified as ##STR76##

EXAMPLE 13

To 200 mls of toluene was added 20 g of bisphenol A and 21.80 g ofdibutyltin oxide. The reaction mixture was heated to boiling and waterof reaction removed using a Dean-Stark head. After all the water hadbeen removed heating was discontinued and the viscous solution allowedto cool to 90° C. To this solution was added 40.73 g of 4-phenoxybenzoylchloride and the mixture heated to reflux for 1 hour. After cooling thewhite crystalline product was collected by filtration, washed with coldtoluene and dried.

Yield 49.71 g 91.5%.

The product was identified as

I claim:
 1. A method for the preparation of an aromatic ester, aromaticthioester, aromatic carbonate, or aromatic thiocarbonate compoundcomprising reacting a first compound of the formula:where each R isindependently a substituted or unsubstituted alkyl or aryl group r is aninteger from 1 to 4 inclusive depending upon the element M used; M is anelement selected from the group consisting of germanium, tin, lead,gallium, indium, thallium, arsenic, antimony, and bismuth; Z¹ is anoxygen or sulphur atom; and A³ is an aromatic, aliphatic,aromatic/aliphatic, heterocyclic, alicyclic, siloxyl or siloxane group,or a hydrogen atomwith a second compound of the formula ##STR78## whereX is a halogen atom or a group capable of reacting with the firstcompound to eliminate a compound containing M and X; Z² is either anoxygen or a sulphur atom; and J is either X or the group A² where A² isan aromatic, aliphatic, aromatic/aliphatic, heterocyclic, alicyclic,siloxyl, or silane group, or the group ##STR79## where A⁴ is anaromatic, aliphatic, aromatic/aliphatic, heterocyclic, alicyclic,siloxyl or silane group,the proportions of the reactants and/or reactionconditions being selected to prevent polymerization and to eliminate thecompound (R)rMX and produce an aromatic ester, aromatic thioester,aromatic carbonate or aromatic thiocarbonate compound of the formula:##STR80## where L is X, the group A², the group ##STR81## or the group##STR82##
 2. A method according to claim 1 wherein the reaction iscarried out in a solvent in which the product is substantially insolubleso that the product precipitates out of solution as it is formed.
 3. Amethod according to claim 1 wherein Z¹ is an oxygen atom.
 4. A methodaccording to claim 1 or 3 wherein Z² is an oxygen atom.
 5. A methodaccording to any one of claims 1 to 4 wherein the stoichiometric ratioof the first compound to the second compound is 1:1.
 6. A methodaccording to claim 5 wherein the second compound is of the formula:##STR83## and the first and second compounds react to produce anaromatic ester, aromatic thioester, aromatic carbonate or aromaticthiocarbonate compound of the formula: ##STR84##
 7. A method accordingto claim 6 wherein the group ##STR85## is bonded to an aromatic group ofA².
 8. A method according to claim 5 wherein the second compound is ofthe formula: ##STR86## and the first and second compounds react toproduce an aromatic ester, aromatic thioester, aromatic carbonate oraromatic thiocarbonate of the formula: ##STR87##
 9. A method accordingto claim 8 wherein the first and second compounds are reacted togetherby gradually adding a solution of the first compound to a solution ofthe second compound.
 10. A method according to claim 1 wherein the firstand second compounds are reacted together in a solvent in which thecompound produced by the reaction is substantially insoluble to that thecompound is precipitated substantially as soon as it is produced.
 11. Amethod according to any one of claim 1 to 4 wherein the second compoundis of the formula: ##STR88## and the first and second compounds arereacted together in a stoichiometric ratio of 2:1 to produce an aromaticester, aromatic thioester, aromatic carbonate or a aromaticthiocarbonate of the formula: ##STR89##
 12. A method according to claim8 wherein the group A⁴ is at least partly aromatic and the groups##STR90## are each bonded to an aromatic group of A⁴.
 13. A methodaccording to claim 12 wherein M is tin.
 14. A method according to claim12 wherein r is
 3. 15. A method according to claim 1 wherein R is abutyl group.
 16. A method according to any one of the preceding claimswherein X is a halogen atom.
 17. A method according to claim 16 whereinx is a chlorine atom.
 18. A method according to claim 12 wherein M istin, lead, or germanium.